Photographic silver halide emulsions



Patented Jan. 9, 1940 rno'roomrmc'sinvnn mum:

nMULsioNs 'Gustav Wilmanns, Wollen, Kreis Bitterteld, and

Wilhelm Schneider, Dessau, Germany, assignors, by mesne assignments, to Ada Ansco Oorporation, Binghamton, N. Y., a corporation of Delaware i 12 Claims. (01. 95-8) UNITED STATES PATENT, OFl lC-E This invention relates to color photography and more particularly to a new and improved photographic material for color forming develop-. ment.

In the manufacture of color transparenciesand color pictures by photography and cinematography it has been proposed to use silver halide emulsions containing dyestuff components. The mode of producing the "color picture differs with the nature of the dyestufl components. In U. S. Patents Nos. 1,102,028 and 1,055,155 dyestufl components are used which yield dyestufl pictures with certain developers by color forming development. For producing multi-color pictures it has been proposed to cast several light-sensitive layers containing difierent coupling components one upon the other and in order to avoid diffusion of the coupling components the light-sensitive layers have been isolated from each other by intermediate layers. It has been shown, however, that this precaution does not prevent the diflusion to the extent required by practice. The problem has been solvedby using dyestuii' components which are fast to diffusion and for the first time a process has been attained by which a'multilayer film yields a color picture by a simple development process (see U. S. Patents 2,179,238;

2,179,244 and 2,178,612 and U. S. applications filed July 15, 1936, Ser. No. 94,340 filed August 5, 1936, Ser. No. 159,518 filed August 17, 1937, Ser. No. 164,499 filed September. 18, 1937.). Further possibilities to render dyestufi components fast to diffusion is to introduce into their molecule a sterol radical or to link up the dyestufl component molecules in a chain like manner.

This invention has for an object to provide a layers containing a dyestufl component made fast to diffusion by the introduction into its molecule of a radical according to this invention.

, Further objects will be seen from the detailed specification following hereafter.

The present invention is based on a process in which especially useful dyestuil formers last todiflusion are obtained by introducing as a substituent into a dyestufl component a compound or derivative of thecyclic menthane group. For

amine, 3-amin0camphor, camphor-3-carboxylic acid, camphane-3-carboxylic acid, camphyl-3- carbinol (German Patent No. 127,855), ketopinic acid (Richter-Anschiltz loc. cit., page 304) or the like. A

In the formulae the numbering of the positions of the camphane nucleus is, as follows:-

Dyestufl components into which these groups may be introduced are for example aand 18- hydroxynaphthoic acids, 2.3-hydroxyanthracene ,carboxylic acid, salicylic acid, hydroxy-fiuorene carboxylic acid, 2.3-hydi'oxycarbazole carboxylic acid, a-naphthol aldehyde, 'aminophenyl methyl pyrazolone, aromatic amines, aminonaphthols. aminonaphthol carboxylic acids, aminonaphthol sulfonic acids, aminophenols, aminobenzoyl acetic acid ester arylides, aminonaphthoyl acetic acid ester arylides, acylacetic acid ester amino- I 'arylides.

The dyestufl components used in the invention may be added to the emulsion'at any point ofits production. The silver halide emulsions thus obtained are especially suitable for the purpose of color photography and may be made into layers in known manner, being applied superimposed on each other on one or both sides of a support. They may be sensitized for various regions' of the spectrum. Emulsions may be applied, however, in another manner, for example the several sensitized emulsions having the different dyestufl formers may be brought on to the support in the form of small particles. The emulsion layers used in the invention may be combined with other layers in which the color picture is produced by a different process, for example by mordant dyeing or by toning. Furthermore, the

emulsion layers of the invention may be combined with other layers which contain other dyestufl formers fast to diffusion as described in the U. S. Patent applications cited hereunder.

The colored pictures may be produced in varioils manners, for example bythe processes of U. S. Patents 2,179,228; 2,179,238; 2,179,244 and 2,178,612 and U. S. applications Ser. No. 94,340, filed August 5, 1936, Ser. No. 141,093 filed May 6, 1937, Ser. No. 159,518 filed August 17, '1937, Ser. No. 164,499 filed September 18, 1937 and Ser. No. 171,705 filed October 29, 1937. Thus the component located in multi-layer film may be converted into azo-dyes following development and fixing by treatment with a diazo compound such as a carbonic acid solution of tetrazotized benzidine disulfonic acid. There is thus produced in each emulsion layer together with a silver picture a dyestufi in which no structure can be perceived by magnification.

azotate silver picture and may be subsequently immersed in a dilute acid solution, whereby a yellow picture is produced consisting of the amdyestuif para camphoryl-aminobenzoyl-acetylaniline-4carboxylic acid azo-p-naphthalene.

Obviously it is also possible to produce a color picture indirectly from. the silver image by, for example, tanning and hardening the gelatin under the image and then producing an azcdyestufi picture at. the non-hardened parts by introducing the layer into a diazonium solution. 2. The chloride of 2.3-hydroxynaphthoic acid is condensed with Z-aminocamphane. The condensation product has the following formula mo l oB-Nn-o i B|C- CH9 11, 0H,. 6

The film is then treated with a silver bleaching out bath, i. e. that described in British Patent 401,340 to produce the dye image.

The exposed emulsion layers may be-developecl by a simple color forming development or by a reversal development as described in U. 53. Patent 2,179,234. Or the picture may be produced in multi-layer material, each layer containing one of said dyestufl components, by exposing the material, developing to black and white, in for instance Amidol, dissolving silver from the negative so produced by bleaching in for example a chromic acid bath, forming images in the remaining silver halide, developing in a developer such as is, used above, iorming silver halideimages .by treatment in a bleaching bath, 1. e. again of 'chromic acid, formingdatent images, transforming the images into silver and color images in a developer capable of forming dyestuffs with said dyestuf! component, removing the developed silver and fixing inthiosuliate. tion of color pictures the silver is generally completely removed. In the production of blackand-white pictures with ,the aid of the silver halide emulsion layers produced in accordance with this invention the silver may be removed or may remain in the layer.

The following examples illustratev the invention:

1. To 1 kilo oi. silver bromide emulsion is added a solution or 3 grams or the sodium salt 01' the condensation product of paramminobenzoylacetyl-aniline-4-carboxylic acid with camphoric acid chloride having the following chemical formula d-o-Nn- -c-on 403 it i Ti H l C 2 L soc- -on= H: I

\ n-o-nn I C-CHr-C- Q o-on i il il and the emulsion is cast to form slayer. This dyestufl former fast to diffusion may be converted into a. color picture in various manners.

The exposed emulsiommay be developed in a solution 0! para-aminodimethyl-aniline. alkaline with sodium carbonate, in which case a In the produc-,

The dyestufi' former fast to diffusion thus obtained is added to a silver halide emulsion which is then converted for example with the aid or'the' silver antidiazotate process into a picture the color of which varies with the antidiazotate se lected. For instance, if the antidiazotate is made from dianisidine there is obtained a'blue violet picture. When the anti-diazotate used is from para-nitraniline pictures of red tints are obtained.

3. 1 (Eij-carboxylphenyl) '-3- (3'-amino-phenyl) fi-pyrazolone is condensed with the chloride of camphane-3-carboxylic acid and the compound produced is added to a silver halide emulsion.

The condensation product has the following formula aiiii obtained. By means of the anti-diazotate processlthis dyestufl former is chiefly suitable for producing yellow tints.

4. 2 hydroxyanthracene 3 carboxylic acid chloride is condensed with camphane-23-diamine and the product is added to a silver halide emulsion. The condensation product has the following formula A layer of this emulsion exposed and developed is treated with a solution of tetrazotized' bnzidine-3.3'-disulfonic acid whereby the whole layer is uniformly dyed blue. If now the layer is further treatedwith the known precautions by the silver bleaching out process there is 'obtained on the portions free from deposited metal a blue dyestufl picture.

' what we claim is: v

1. A silver halide emulsion for color photography containing a dyestufi component fast to diffusion, said dyestuff component being capable of forming a dye with the oxidation product of a developer and containing inits molecule a radical having substantially the chemical structure of a saturated bicyclic terpene having a dimethyl ture of a saturated bicyclic terpene having a dimethyl substituted carbon atom as the bridge common to the rings, and another radical capable of preventing diffusion of said dyestufl component. 1 I

3. A silver halide emulsion for color photography containing a dyestuff component fast to diflusion, said dyestufl component being capable of forming a dye with the oxidation product of a developer and containing in its molecule a molecule a radical having substantially the chemical structure of a saturated bicyclic terpene having a dimethyl substituted carbon atom as the bridge common to the rings.

v 5. A silver halide emulsion for color photography containing a dyestu'ff component fast to diffusion, said dyestuif component being capable of forming a dye with the oxldationproductof of forming a dye with the oxidation product of V a developer, and containing in its molecule .an

a developer, and containing in its molecule a radical having substantially the chemical structure of a saturated bicycfic terpene having a dimethyl substituted carbona'tom as the bridge common to the rings, said terpene radical being linked to the dyestuif forming radical by means of an acid amide linking;

-6. A silver halide emulsion 'for color photoga amino group substituted by a carboxylic acid of a saturated bicyclic terpene having a dimethyl substituted carbonatom'asthe bridge common 15 I to the rings.

'7. A silver halide emulsion for color photography containing a dyestuif component fast to diffusion, said dyestuif component being capable acid radical substituted by an amine of a saturated bicyclic terpene having a dimethyl substituted carbon atom as the bridge common to the rings. 8. A silver halide emulsion for color photog- I raphy containing a dyestufl component fast to diffusion, said dyestufl component being capable of forming a dye with the oxidation product of a developer, and capable of coupling with the formation of an azo dye, and containing in its molecule a radicle selected from the class consisting of those having substantially the chemical structure of ajsaturated bicyclic terpene having a dimethyl substituted carbon atom as the bridge common to the rings and camphoric acid.

9. The emulsion as defined in claim 8, wherein the radicle. is a radicle of a camphane. v

10. The silver halide-emulsion as defined in claim 8 wherein the dyestuff component is a condensation product of para-aminobenzoylacetyl-aniline-4-carboxylic acid with amphoric acid chloride.

11. The silver halide emulsionas defined. in claim 8, wherein the dyestufl component is the condensation product of the chloride of 2.3-hydroxynaphthoic acid with 2-aminocamphane.

12. A silver halide emulsion as defined in claim 8, wherein the dyestuff component is the Y condensation product of a pyrazolone with the U0 chloride of camphane-S-carboxylic acid.

some 

